CN104030312B - A kind of synthetic method of titanium-silicon molecular sieve TS-1 - Google Patents
A kind of synthetic method of titanium-silicon molecular sieve TS-1 Download PDFInfo
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- CN104030312B CN104030312B CN201410195026.6A CN201410195026A CN104030312B CN 104030312 B CN104030312 B CN 104030312B CN 201410195026 A CN201410195026 A CN 201410195026A CN 104030312 B CN104030312 B CN 104030312B
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Abstract
The invention discloses a kind of synthetic method of TS-1 HTS, titanium source is hydrolyzed under organosilyl existence, and its hydrolysis rate is reduced to and mates with silicon source hydrolysis rate; Silicon source and titanium source be the rear short mix of parallel hydrolysis respectively, avoids the formation of extra-framework titanium, does not need to add alcohol; Appropriate regulation crystallization condition, achieve the effective control to zeolite crystal size, grain size distribution reaches unanimity, and solves conventional art and easily forms extra-framework titanium, needs except alcohol, feed rate are slow, zeolite crystal size is not easy the problems such as control.Have the advantages that production process is easy, reproducible.
Description
Technical field
The invention belongs to inorganic chemistry and product technical field, relate to a kind of synthetic method of titanium-silicon molecular sieve TS-1.
Background technology
HTS is a kind of extraordinary molecular sieve containing titanium atom in framework of molecular sieve, and nineteen eighty-three Tramasso has synthesized the titanium-silicon molecular sieve TS-1 with MFI topological framework first.Titanium-silicon molecular sieve TS-1 has very high thermostability, resistance to acid, hydrophobicity, good catalytic activity and selectivity, especially under low temperature and condition of normal pressure, to the liquid phase oxidation reaction (light base, ketone ammonia oxidation etc. as the oxidation of alkane, alkene epoxidation, alcohol oxidation, benzene and phenol) of the gas chromatography taking industrial grade hydrogen peroxide as oxygenant, there is unique shape selective catalysis function, and can not deep oxidation and contaminate environment, be thus called the green catalyst with " atom economy " feature.
The synthesis of the first public TS-1 of US4410501, it adopts water heat transfer, silicon source, titanium source, template are configured to gel precursor, then obtained gel precursor is joined band stir titanium autoclave in hydrothermal crystallizing, then filter, wash, drying and roasting obtain product TS-1 molecular sieve.The method needs the operation of extreme care, extremely easily occurs extra-framework titanium.
CN1401569A discloses a kind of fast synthesis method of nano-titanium silicalite molecular sieve catalyst, it makes 4-propyl bromide by oneself to exchange through strongly basic anionic resin, concentrating and obtaining the TPAOH aqueous solution is template, tetraethoxy is silicon source, tetrabutyl titanate is titanium source, in hydrothermal crystallizing system, template is added to by a certain percentage in estersil and titanium ester, abundant hydrolysis, mixing, reaction is except alcohol 3-6h, again by Ti-Si sol crystallization 12-24h, obtained brilliant looks are cubes, crystal grain is even, size is at the titanium-silicon molecular sieve catalyst of about 100nm.But hydrolysis time needs strict control, and synthesis needs except alcohol, concerning industrial production, be very difficult to operation.
CN1418813A discloses a kind of method of quick synthesis of titanium silicon molecular sieve, be titanium source by adopting with tetrabutyl titanate, with tetraethyl orthosilicate or silicon sol for silicon source, with quaternary ammonium hydroxide or/and organic amine is template, the technical scheme of adding phosphoric acid in reaction process solves the long problem of titanium silicon generated time preferably.But be very easy to form extra-framework titanium in its building-up process, and its crystal grain is difficult to accomplish to be less than 200nm.
CN102464331A discloses a kind of method adopting organosilicon synthesizing small-crystallite titanium-silicon molecular sieve, what adopt is two (triethoxy is silica-based) methane, owner of a right a surname be called small crystal grain molecular sieve, but the example unexpectedly crystal grain up to several microns, be larger crystal molecular sieve completely.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of TS-1 HTS, solve conventional art and easily form extra-framework titanium, need except alcohol, feed rate are slow, zeolite crystal size is not easy the problems such as control.Have the advantages that production process is easy, reproducible.
The technical solution used in the present invention is as follows:
A synthetic method for titanium-silicon molecular sieve TS-1, comprises the following steps:
1) silicon source and template and water mixed hydrolysis obtain silicon source hydrolyzate, and titanium source and organosilicon and template and water mixed hydrolysis obtain titanium source hydrolyzate;
2) low temperature plastic is carried out by after described titanium source hydrolyzate and silicon source hydrolyzate short mix;
3) after low temperature cemented into bundles, pass into liquefied ammonia or ammoniacal liquor, heat up crystallization subsequently again;
4) crystallization product obtains titanium-silicon molecular sieve TS-1 after roasting.
Step 1) described in template comprise TPA
+.
Step 1) in titanium source, silicon source, template and water mol ratio be (0.01 ~ 0.05): 1:(0.10 ~ 0.30): (13 ~ 25).
One in described silicon source employing methyl silicate, tetraethyl silicate, butyl silicate or its mixture, the hydrolysis of silicon source adopts acid hydrolysis or adopts basic hydrolysis.
Described silicon source adopts tetraethyl silicate 28, ethyl silicate 40, silicon source and TPAOH and 4-propyl bromide mixed hydrolysis.
Described titanium source is one in butyl (tetra) titanate, titanium ethanolate or its mixture.
Described organosilicon is one in dimethyldiethoxysilane, three aminopropyl triethyl TMOSs or its mixture, and titanium source and organosilyl mol ratio are 1:0.5 ~ 1:6.
Described titanium source hydrolyzate and the direct short mix of silicon source hydrolyzate, without plastic direct except alcohol step.
The gelling temperature of described low temperature plastic is 0 ~ 80 DEG C.
Proceed to reactor after described titanium source hydrolyzate mixes plastic with silicon source hydrolyzate, pass into liquefied ammonia, regulate colloid pH to 8 ~ 13, under autogenous pressure, be warming up to 140 ~ 185 DEG C of crystallization 65 ~ 80h.
Described crystallization product through being separated, washing, after drying, 480 ~ 600 DEG C of roasting 2 ~ 6h.
The present invention contrasts prior art, has following advantage:
Titanium source is hydrolyzed under organosilyl existence, and its hydrolysis rate is reduced to and mates with silicon source hydrolysis rate; Silicon source and titanium source be the rear short mix of parallel hydrolysis respectively, avoids the formation of extra-framework titanium, does not need to add alcohol; Appropriate regulation crystallization condition, achieve the effective control to zeolite crystal size, grain size distribution reaches unanimity, and adds catalytic activity point position, and catalytic activity point position layout is more reasonable, and feed rate also improves thereupon, is conducive to suitability for industrialized production; Molecular sieve the present invention prepared is used for the ammonia oxidation of pimelinketone, excellent property, and catalyzed reaction material mean residence time is on a catalyst more homogeneous, significantly improves activity and the Technical Economy thereof of catalyzer.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the embodiment of the present invention 1 gained catalyzer, and X-coordinate is 2 θ diffraction angle, and ordinate zou is diffraction peak intensity;
Fig. 2 is the scanning electron microscope sem figure of the embodiment of the present invention 1 gained catalyzer;
Fig. 3 is the UV-vis spectrogram of the embodiment of the present invention 1 gained catalyzer, and X-coordinate is ultraviolet-visible wavelength, and ordinate zou is ultravioletvisible absorption intensity;
Fig. 4 is the XRD spectra of the embodiment of the present invention 2 gained catalyzer, and X-coordinate is 2 θ diffraction angle, and ordinate zou is diffraction peak intensity;
Fig. 5 is the scanning electron microscope sem figure of the embodiment of the present invention 2 gained catalyzer;
Fig. 6 is the UV-vis spectrogram of the embodiment of the present invention 2 gained catalyzer, and X-coordinate is ultraviolet-visible wavelength, and ordinate zou is ultravioletvisible absorption intensity.
Embodiment
Below by embodiment, the present invention is further elaborated, but scope of the present invention has more than and is limited to following explanation.
The method of the analysis and calculation adopted in the present invention is:
The pimelinketone molar weight of transformation efficiency (%)=(after pimelinketone molar weight-reaction that reaction drops into remaining pimelinketone the molar weight)/reaction input of pimelinketone
Peak area/(peak area of the peak area+by product of cyclohexanone-oxime) embodiment 1 of selectivity (the %)=cyclohexanone-oxime of cyclohexanone-oxime:
The mixing solutions of TPAOH and 4-propyl bromide that 50g ethyl silicate 40 adds requirement is hydrolyzed, and becomes clear gum thing, for subsequent use.6.4g butyl (tetra) titanate and the 2.5g dimethyldiethoxysilane mixture mixing solutions of 25ml TPAOH and 4-propyl bromide are hydrolyzed, molar ratio of material is: TiO
2: SiO
2: TPA
+: H
2o=0.05:1:0.35:20.
Then by the 0 DEG C of rapid stirring mixing of above-mentioned two kinds of hydrolyzed solutions, proceed in Autoclaves for synthesis (about 0.1Mpa), continue stirring 2 hours, passing into liquefied ammonia regulates pH to be 13, be warming up to 170 DEG C of crystallization 48 hours, separation, washing, drying, then 550 DEG C of roastings 5 hours, obtain product HTS, its XRD spectra, scanning electron microscope sem figure and UV-vis spectrogram are as shown in Fig. 1,2 and 3.
As can be seen from Fig. 1, in 2 θ=25.4, a ° place does not show XRD peak to this sieve sample, and in Fig. 3, absorption peak more weak near 330nm, all illustrates in this sieve sample and do not have extra-framework titanium species to be formed.As can be seen from Figure 2, gained zeolite crystal even size distribution is consistent.
Comparative example 1:
The mixing solutions of TPAOH and 4-propyl bromide that 50g ethyl silicate 40 adds requirement is hydrolyzed, and becomes clear gum thing, for subsequent use.6.4g butyl (tetra) titanate and the 3.7g tri-aminopropyl triethyl TMOS mixture mixing solutions of 25ml TPAOH and 4-propyl bromide are hydrolyzed, molar ratio of material is: TiO
2: SiO
2: TPA
+: H
2o=0.05:1:0.35:20.
Then by the 0 DEG C of rapid stirring mixing of above-mentioned two kinds of hydrolyzed solutions, proceed in Autoclaves for synthesis (about 0.1Mpa), continue stirring 2 hours, passing into liquefied ammonia regulates pH to be 13, be warming up to 170 DEG C of crystallization 48 hours, separation, washing, drying, then 550 DEG C of roastings 5 hours, obtain product HTS.
Embodiment 2:
The mixing solutions of TPAOH and 4-propyl bromide that 50g tetraethyl silicate 28 adds requirement is hydrolyzed, and becomes clear gum thing, for subsequent use.2g butyl (tetra) titanate and the 2.5g dimethyldiethoxysilane mixture mixing solutions of 25ml TPAOH and 4-propyl bromide are hydrolyzed, molar ratio of material is: TiO
2: SiO
2: TPA
+: H
2o=0.025:1:0.35:20.
Then by the 0 DEG C of rapid stirring mixing of above-mentioned two kinds of hydrolyzed solutions, proceed in Autoclaves for synthesis (about 0.1Mpa), continue stirring 2 hours, pass into liquefied ammonia and regulate pH to be 13, be warming up to 170 DEG C of crystallization 24 hours.
By crystallization product separation, washing, drying, then 550 DEG C of roastings 5 hours, obtain product HTS, its XRD spectra, scanning electron microscope sem figure and UV-vis spectrogram are as shown in Fig. 4,5 and 6.
As can be seen from Fig. 4, this sieve sample has more weak XRD peak at a ° place, 2 θ=25.4, and in Fig. 6, has certain absorption peak near 330nm, all illustrates in this sieve sample to there are a certain amount of extra-framework titanium species.But as can be seen from Figure 5, gained zeolite crystal even size distribution is consistent.
Embodiment 3:
The mixing solutions of TPAOH and 4-propyl bromide that 50g ethyl silicate 40 adds requirement is hydrolyzed, and becomes clear gum thing, for subsequent use.6.4g butyl (tetra) titanate and the 2.5g dimethyldiethoxysilane mixture mixing solutions of 25ml TPAOH and 4-propyl bromide are hydrolyzed, molar ratio of material is: TiO
2: SiO
2: TPA
+: H
2o=0.025:1:0.35:20.
Then by above-mentioned two kinds of hydrolyzed solutions under 25 DEG C of conditions, rapid stirring mixes, and proceeds in Autoclaves for synthesis (about 0.1Mpa), continues stirring 2 hours, passes into liquefied ammonia and regulates pH to be 13, be warming up to 170 DEG C of crystallization 24 hours.
By crystallization product separation, washing, drying, then 550 DEG C of roastings 5 hours, obtain product HTS.
Embodiment 4:
The mixing solutions of TPAOH and 4-propyl bromide that 50g ethyl silicate 40 adds requirement is hydrolyzed, and becomes clear gum thing, for subsequent use.6.4g butyl (tetra) titanate and the 2.5g dimethyldiethoxysilane mixture mixing solutions of 25ml TPAOH and 4-propyl bromide are hydrolyzed, molar ratio of material is: TiO
2: SiO
2: TPA
+: H
2o=0.025:1:0.35:20.
Then by above-mentioned two kinds of hydrolyzed solutions under 75 DEG C of conditions, rapid stirring mixes, and proceeds in Autoclaves for synthesis (about 0.1Mpa), continues stirring 2 hours, passes into liquefied ammonia and regulates pH to be 13, be warming up to 170 DEG C of crystallization 24 hours.
By crystallization product separation, washing, drying, then 550 DEG C of roastings 5 hours, obtain product HTS.
Embodiment 5:
The mixing solutions of TPAOH and 4-propyl bromide that 50g ethyl silicate 40 adds requirement is hydrolyzed, and becomes clear gum thing, for subsequent use.6.4g butyl (tetra) titanate and the 2.5g dimethyldiethoxysilane mixture mixing solutions of 25ml TPAOH and 4-propyl bromide are hydrolyzed, molar ratio of material is: TiO
2: SiO
2: TPA
+: H
2o=0.025:1:0.35:20.
Then by above-mentioned two kinds of hydrolyzed solutions under 0 DEG C of condition, rapid stirring mixes, and proceeds in Autoclaves for synthesis (about 0.1Mpa), continues stirring 2 hours, passes into liquefied ammonia and regulates pH to be 12, be warming up to 170 DEG C of crystallization 24 hours.
By crystallization product separation, washing, drying, then 550 DEG C of roastings 5 hours, obtain product HTS.
Embodiment 6
The mixing solutions of TPAOH and 4-propyl bromide that 50g tetraethyl silicate 28 adds requirement is hydrolyzed, and becomes clear gum thing, for subsequent use.2g butyl (tetra) titanate and the 2.5g dimethyldiethoxysilane mixture mixing solutions of 25ml TPAOH and 4-propyl bromide are hydrolyzed, molar ratio of material is: TiO
2: SiO
2: TPA
+: H
2o=0.025:1:0.20:20.
Then by the 0 DEG C of rapid stirring mixing of above-mentioned two kinds of hydrolyzed solutions, proceed in Autoclaves for synthesis (about 0.1Mpa), continue stirring 2 hours, pass into liquefied ammonia and regulate pH to be 8, be warming up to 170 DEG C of crystallization 24 hours.
By crystallization product separation, washing, drying, then 550 DEG C of roastings 5 hours, obtain product HTS.
Comparative example 2
50g ethyl silicate 40, the mixing solutions of the TPAOH and 4-propyl bromide that add requirement is hydrolyzed, and becomes clear gum thing, for subsequent use.After being dissolved with 90mL Virahol by 6.4g butyl (tetra) titanate, the mixing solutions adding 25ml TPAOH and 4-propyl bromide is hydrolyzed, and material mole is: TiO
2: SiO
2: TPA
+: H
2o=0.05:1:0.35::20.
Then by above-mentioned two kinds of hydrolyzed solutions 0 DEG C rapid stirring mixing, proceed in Autoclaves for synthesis (about 0.1Mpa), after be warming up to 170 DEG C of crystallization 48 hours.
By crystallization product separation, washing, drying, then 550 DEG C of roastings 5 hours, obtain product HTS.
Embodiment 7
Distinguish gained HTS in Example 1 to 6 and comparative example 1 to 2 and be used for ammoxidation of cyclohexanone reaction, reaction conditions: TS-1 catalyzer 1.5g, pimelinketone 15.2g, water 15g, trimethyl carbinol 38g, 25% ammoniacal liquor 22.9g, after being heated to temperature of reaction 80 DEG C, add 30% hydrogen peroxide 24g, react after 5 hours, the selectivity measuring the transformation efficiency of pimelinketone and cyclohexanone-oxime is as shown in the table:
| Pimelinketone transformation efficiency % | The selectivity % of oxime | |
| Embodiment 1 | 99.2 | 99.0 |
| Embodiment 2 | 94.0 | 92.5 |
| Embodiment 3 | 98.3 | 97.8 |
| Embodiment 4 | 97.4 | 97.6 |
| Embodiment 5 | 98.6 | 98.4 |
| Embodiment 6 | 92.0 | 93.1 |
| Comparative example 1 | 78.3 | 80.1 |
| Comparative example 2 | 78.5 | 79.5 |
As can be seen from table, the transformation efficiency of pimelinketone and the selectivity of cyclohexanone-oxime can be made all to reach more than 92% by the TS-1 molecular sieve regulating material ratio, gelling temperature, glue pH to obtain.
Claims (8)
1. a synthetic method for titanium-silicon molecular sieve TS-1, comprises the following steps:
1) silicon source and template and water mixed hydrolysis obtain silicon source hydrolyzate, titanium source and organosilicon and template and water mixed hydrolysis obtain titanium source hydrolyzate, described organosilicon is one in dimethyldiethoxysilane, three aminopropyl triethyl TMOSs or its mixture, and described titanium source and organosilyl mol ratio are 1:0.5 ~ 1:6;
2) carry out low temperature plastic by after described titanium source hydrolyzate and silicon source hydrolyzate short mix, the gelling temperature of described low temperature plastic is 0 ~ 80 DEG C;
3) after low temperature cemented into bundles, pass into liquefied ammonia or ammoniacal liquor, regulate colloid pH to 8 ~ 13, heat up crystallization subsequently again;
4) crystallization product obtains titanium-silicon molecular sieve TS-1 after roasting.
2. the synthetic method of titanium-silicon molecular sieve TS-1 as claimed in claim 1, it is characterized in that, described template comprises TPA
+.
3. the synthetic method of titanium-silicon molecular sieve TS-1 as claimed in claim 1, is characterized in that, the mol ratio of described titanium source, silicon source, template and water is 0.01 ~ 0.05:1:0.10 ~ 0.30:13 ~ 25.
4. the synthetic method of titanium-silicon molecular sieve TS-1 as claimed in claim 1, is characterized in that, the one in described silicon source employing methyl silicate, tetraethyl silicate, butyl silicate or its mixture, the hydrolysis of silicon source adopts acid hydrolysis or adopts basic hydrolysis.
5. the synthetic method of titanium-silicon molecular sieve TS-1 as claimed in claim 4, is characterized in that, described silicon source adopts tetraethyl silicate 28, ethyl silicate 40, silicon source and TPAOH and 4-propyl bromide mixed hydrolysis.
6. the synthetic method of titanium-silicon molecular sieve TS-1 as claimed in claim 1, is characterized in that, described titanium source is one in butyl (tetra) titanate, titanium ethanolate or its mixture.
7. the synthetic method of titanium-silicon molecular sieve TS-1 as claimed in claim 1, is characterized in that, proceed to reactor, pass into liquefied ammonia, be warming up to 140 ~ 185 DEG C of crystallization 65 ~ 80h under autogenous pressure after described titanium source hydrolyzate mixes plastic with silicon source hydrolyzate.
8. the synthetic method of titanium-silicon molecular sieve TS-1 as claimed in claim 1, is characterized in that, described crystallization product through being separated, washing, after drying, 480 ~ 600 DEG C of roasting 2 ~ 6h.
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| CN106829996B (en) * | 2015-12-03 | 2019-03-15 | 中国石油大学(华东) | A kind of Titanium Sieve Molecular Sieve and preparation method thereof |
| CN106006665B (en) * | 2016-05-13 | 2018-08-21 | 浙江师范大学 | A kind of preparation method of titanium-silicon molecular sieve TS-1 |
| CN106745039B (en) * | 2016-12-29 | 2019-01-29 | 中国科学院上海硅酸盐研究所 | A kind of size adjustable and the nanometer Ti-Si zeolite molecular sieve and preparation method thereof with ultra-high yield |
| CN111994918B (en) * | 2020-08-27 | 2021-09-21 | 宁夏美邦寰宇化学有限公司 | Preparation method and preparation system of titanium silicalite molecular sieve catalyst |
| CN113683097B (en) * | 2021-09-23 | 2023-04-04 | 深圳科冠华太新材料技术有限公司 | Preparation method of TS-1 molecular sieve rich in framework four-coordinate titanium |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| CN101190792A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Method for synthesizing titanium-silicon molecular screen |
-
2014
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| CN101190792A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Method for synthesizing titanium-silicon molecular screen |
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